CN104527177B - A kind of recyclable prepreg, cured sheets, copper-clad plate and its preparation for printed circuit board (PCB), recovery method - Google Patents
A kind of recyclable prepreg, cured sheets, copper-clad plate and its preparation for printed circuit board (PCB), recovery method Download PDFInfo
- Publication number
- CN104527177B CN104527177B CN201410781355.9A CN201410781355A CN104527177B CN 104527177 B CN104527177 B CN 104527177B CN 201410781355 A CN201410781355 A CN 201410781355A CN 104527177 B CN104527177 B CN 104527177B
- Authority
- CN
- China
- Prior art keywords
- group
- alkenylene
- alkylene
- hydrocarbylene
- alkynylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000011084 recovery Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000011889 copper foil Substances 0.000 claims abstract description 55
- 239000012779 reinforcing material Substances 0.000 claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims description 98
- 229920000647 polyepoxide Polymers 0.000 claims description 98
- 239000003292 glue Substances 0.000 claims description 67
- 125000004450 alkenylene group Chemical group 0.000 claims description 53
- 125000002947 alkylene group Chemical group 0.000 claims description 39
- 125000004419 alkynylene group Chemical group 0.000 claims description 37
- 239000007787 solid Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 29
- 238000006731 degradation reaction Methods 0.000 claims description 28
- 230000015556 catabolic process Effects 0.000 claims description 27
- 125000001072 heteroaryl group Chemical group 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 26
- 239000003365 glass fiber Substances 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- -1 aliphatic carboxylate anions Chemical class 0.000 claims description 19
- 125000003342 alkenyl group Chemical group 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000000732 arylene group Chemical group 0.000 claims description 18
- 125000005724 cycloalkenylene group Chemical group 0.000 claims description 18
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 18
- 125000000623 heterocyclic group Chemical group 0.000 claims description 17
- 125000000304 alkynyl group Chemical group 0.000 claims description 16
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 239000007857 degradation product Substances 0.000 claims description 13
- 125000005549 heteroarylene group Chemical group 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 11
- 150000001721 carbon Chemical group 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 7
- 239000002657 fibrous material Substances 0.000 claims description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 6
- MHQSYLJLQJENAQ-UHFFFAOYSA-N 2-phenylethane-1,1-diol Chemical compound OC(O)CC1=CC=CC=C1 MHQSYLJLQJENAQ-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 125000005343 heterocyclic alkyl group Chemical group 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 125000002070 alkenylidene group Chemical group 0.000 claims description 4
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002312 hydrocarbylidene group Chemical group 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 claims description 2
- YWMLORGQOFONNT-UHFFFAOYSA-N [3-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC(CO)=C1 YWMLORGQOFONNT-UHFFFAOYSA-N 0.000 claims description 2
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002318 adhesion promoter Substances 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 239000002082 metal nanoparticle Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 2
- 239000013008 thixotropic agent Substances 0.000 claims description 2
- 239000012745 toughening agent Substances 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000002087 whitening effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000004593 Epoxy Substances 0.000 abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 30
- 229920005989 resin Polymers 0.000 description 25
- 239000011347 resin Substances 0.000 description 25
- 239000000843 powder Substances 0.000 description 22
- 238000001816 cooling Methods 0.000 description 21
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 19
- 239000003063 flame retardant Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 239000004744 fabric Substances 0.000 description 16
- 239000011521 glass Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 238000003825 pressing Methods 0.000 description 12
- 239000006087 Silane Coupling Agent Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 11
- 238000002791 soaking Methods 0.000 description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 10
- 229910052794 bromium Inorganic materials 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 229920001187 thermosetting polymer Polymers 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229920006037 cross link polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 125000005160 aryl oxy alkyl group Chemical group 0.000 description 3
- 238000003486 chemical etching Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- NLXGURFLBLRZRO-UHFFFAOYSA-N 1-chloro-2-(2-chloroethoxymethoxy)ethane Chemical compound ClCCOCOCCCl NLXGURFLBLRZRO-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- 125000004036 acetal group Chemical group 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 2
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- LYWVNPSVLAFTFX-UHFFFAOYSA-N 4-methylbenzenesulfonate;morpholin-4-ium Chemical compound C1COCCN1.CC1=CC=C(S(O)(=O)=O)C=C1 LYWVNPSVLAFTFX-UHFFFAOYSA-N 0.000 description 1
- 238000006087 Brown hydroboration reaction Methods 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229960002216 methylparaben Drugs 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B19/00—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica
- B32B19/02—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica the layer of fibres or particles being impregnated or embedded in a plastic substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B19/00—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica
- B32B19/04—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica next to another layer of the same or of a different material
- B32B19/041—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica next to another layer of the same or of a different material of metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/10—Removing layers, or parts of layers, mechanically or chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/18—Handling of layers or the laminate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/54—Amino amides>
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/018—Additives for biodegradable polymeric composition
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/012—Flame-retardant; Preventing of inflammation
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/17—Post-manufacturing processes
- H05K2203/178—Demolishing, e.g. recycling, reverse engineering, destroying for security purposes; Using biodegradable materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Mechanical Engineering (AREA)
- Epoxy Resins (AREA)
- Laminated Bodies (AREA)
Abstract
The applicant provides a kind of recyclable prepreg for printed circuit board (PCB) and recyclable cured sheets, including degradable epoxy resin-base and reinforcing material；The applicant additionally provides a kind of recyclable copper-clad plate for printed circuit board (PCB), including copper foil and recyclable prepreg；The recyclable copper-clad plate, it is doubling plate or multi-layer sheet, is prepared by recyclable prepreg and copper foil overlapping.Copper-clad plate prepared by the present invention can both reach property indices, and easily recovery, and recovery method has the advantages that gentle reaction condition, economy, is easily controlled.
Description
Technical Field
The invention relates to the technical field of epoxy resin composite materials, in particular to a recyclable epoxy resin composite material.
Background
The main raw materials of the copper-clad plate composite material comprise copper foil, reinforced fiber cloth, epoxy resin, a curing agent, an accelerator, a solvent, a filler and the like, and are closely related to the technological property, the processing property and the comprehensive property of a final product in the production process of the copper-clad plate. The laminated board with metal copper foil coated on one or two surfaces of the substrate is called copper clad board, mainly used for manufacturing printed circuit board, widely applied to products such as communication, mobile communication, computer, instrument and meter, digital television, numerical control sound, satellite, radar and the like, and also applied to the new product fields such as solar battery, LED illumination, LED backlight source, flat panel display, automobile electronic and the like in recent years. In the electronic whole machine product, the copper-clad plate plays three roles of element load, circuit interconnection and circuit insulation.
The epoxy resin is widely applied to the copper-clad plate due to excellent processing performance before curing, excellent adhesive force after curing, mechanical strength, heat dispersibility, electrical performance, chemical resistance and the like. In addition, the high density, three-dimensional network structure of the cured epoxy resin makes it an extremely durable and hard material that can withstand a wide range of environmental conditions. At the same time, the crosslinked network structure of the cured epoxy resin makes its removal, recycling and reuse particularly difficult. In essence, the crosslinking reaction which normally occurs with compounding polyamines with epoxy resins is irreversible, and therefore, this substance cannot be re-melted, cannot be re-shaped without damage, and cannot be easily dissolved.
The thermosetting epoxy resin, the copper foil and the fiber are combined to prepare a copper-clad plate and can be applied to the field of Printed Circuit Boards (PCBs), and the PCB manufacturing process flow generally goes through the processes of film plate making, pattern transfer, chemical etching, via hole and copper foil treatment, soldering aid, solder resist and the like. The cured epoxy resin is difficult to decompose and melt, and accordingly, the epoxy resin-based circuit board is inconvenient to recycle.
The recovery processing technology of waste printed circuit boards at home and abroad mainly comprises three types: one is a wet processing technique. Including acid pickling, corrosion, etc.; second, the pyrogenic process treatment technology, including burning, cracking, direct smelting, etc.; and thirdly, a physical mechanical treatment technology comprising the working procedures of crushing, sorting and the like. Generally, the methods have limitations in different degrees, the treatment scale of the pyrogenic process technology is the largest, the recovery rate of the wet process technology to metal is higher, but the wet process and the pyrogenic process treatment technologies have serious environmental pollution and large environmental protection cost investment; the physical mechanical treatment method is low in investment and capable of recovering metals, but cannot realize recovery of fibers and resins. Therefore, the method for recycling the waste materials, which is environmentally friendly, effective and feasible, is still a problem to be solved in the field of materials.
Disclosure of Invention
Aiming at the problems in the prior art, the applicant provides a recyclable copper-clad plate for a printed circuit board and a preparation and recycling method thereof. The copper-clad plate prepared by the invention can reach various performance indexes and is easy to recover, and the recovery method has the advantages of mild reaction conditions, economy, easy control and the like.
The technical scheme of the invention is as follows:
the applicant provides a recyclable prepreg and a recyclable prepreg for a printed circuit board, which comprise a degradable epoxy resin matrix and a reinforcing material.
The applicant also provides a recyclable copper-clad plate for a printed circuit board, which comprises a copper foil and a recyclable prepreg. The recyclable copper-clad plate is a double-layer plate or a multilayer plate and is prepared by laminating a recyclable prepreg and a copper foil.
The degradable epoxy resin matrix comprises epoxy resin and a degradable curing agent.
The degradable curing agent is one or more of the degradable curing agents with the following molecular structure general formula:
(1)
wherein,
r1 is one of a hydrogen atom, alkyl group, cycloalkyl group, heterocyclic group, heterocycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, heteroaryl group, alkylheteroalkyl group, alkynyl group, hydrocarbylene group, hydrocarbyleneheteroalkylene group, alkenylene group, hydrocarbyleneheteroalkylene group, alkynylene group, or hydrocarbyleneheteroalkylene group;
r2 is one of a hydrogen atom, alkyl group, cycloalkyl group, heterocyclic group, heterocycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, heteroaryl group, alkylheteroalkyl group, alkynyl group, hydrocarbylene group, hydrocarbyleneheteroalkylene group, alkenylene group, hydrocarbyleneheteroalkylene group, alkynylene group, or hydrocarbyleneheteroalkylene group;
r1 and R2 may be the same or different;
r1 and R2 may also be in the same ring structure with the common adjacent carbon atom;
a is one of an arylidene group, a hydrocarbylidene arylidene group, an alkenylidene arylidene group, an alkynylidene arylidene group, a heteroaromatic group, a hydrocarbylidene heteroaromatic group, an alkenylidene heteroaromatic group, and an alkynylidene heteroaromatic group;
b is one of an arylidene group, a hydrocarbylidene arylidene group, an alkenylidene arylidene group, an alkynylidene arylidene group, a heteroaromatic group, a hydrocarbylidene heteroaromatic group, an alkenylidene heteroaromatic group and an alkynylidene heteroaromatic group;
a and B may be the same or different;
r3 is
R4 is
R3 and R4 may be the same or different;
r5 is one of hydrogen atom, alkyl, cycloalkyl, heterocyclic group, heterocyclic alkyl, alkenyl, cycloalkenyl, aryl, heteroaryl, alkoxyalkyl or alkynyl;
r6 is one of hydrogen atom, alkyl, cycloalkyl, heterocyclic group, heterocyclic alkyl, alkenyl, cycloalkenyl, aryl, heteroaryl, alkoxyalkyl or alkynyl;
r5 and R6 may be the same or different;
Xn-is one of C1-C10 aliphatic carboxylate anions, C1-C10 alicyclic carboxylate anions, aromatic carboxylate anions and heterocyclic aromatic carboxylate anions;
n is 1, 2 or 3;
m is 0.1 to 3;
y is one of Lewis acids;
(2)
wherein,
p1 is one of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, an alkylheteroalkyl group, an alkynyl group, a hydrocarbylene group, a hydrocarbyleneheteroalkylene group, an alkenylene group, a hydrocarbyleneheteroalkylene group, an alkynylene group, or a hydrocarbyleneheteroalkynylene group;
p2 is one of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, an alkylheteroalkyl group, an alkynyl group, a hydrocarbylene group, a hydrocarbyleneheteroalkylene group, an alkenylene group, a hydrocarbyleneheteroalkylene group, an alkynylene group, or a hydrocarbyleneheteroalkynylene group;
p1 and P2 may be the same or different;
p1 and P2 may also be in the same ring structure with the common adjacent carbon atom;
c is alkylene, hydrocarbylene heteroalkylene, alkenylene heteroalkenylene, hydrocarbylene heteroalkenylene, alkynylene, cycloalkylene, hydrocarbylene cycloalkylene alkylene, alkenylene cycloalkylene, hydrocarbylene cycloalkylene alkenylene, alkynylene cycloalkylene alkynylene, heterocyclic alkylene, hydrocarbylene heterocyclic alkylene, alkenylene heterocyclic alkylene, hydrocarbylene heterocyclic alkylene, alkynylene heterocyclic alkylene, alkenylene cycloalkylene, cycloalkenylene alkenylene, heterocyclic alkylene, heterocyclylene alkylene, cycloalkylene, heterocyclylene, cycloalkenylene, alkenylene, cycloalkenylene alkenylene, alkenylene, heterocyclylene alkenylene, alkynylene cycloalkenylene, heterocyclylene alkenylene, heterocyclylene alkylene heterocyclylene, heterocyclylene alkylene, cycloalkylene, alkenylene, heterocyclylene, cycloalkylene, cycloalkenylene, cycloalkylene, heterocyclylene, alkynylene, heterocyclylene, cycloalkenylene, cycloalkylene, cycloalkenylene, One of a hydrocarbylene heterocycloalkenylene, an arylene, a hydrocarbylene arylene, a heteroarylene, a hydrocarbylene heteroarylene, and a hydrocarbylene heteroarylene alkynylene;
d is alkylene, hydrocarbylene heteroalkylene, alkenylene heteroalkenylene, hydrocarbylene heteroalkenylene, alkynylene, cycloalkylene, hydrocarbylene cycloalkylene, alkenylene cycloalkylene, hydrocarbylene cycloalkylene alkenylene, alkynylene cycloalkylene alkynylene, heterocyclic alkylene, hydrocarbylene heterocyclic alkylene, alkenylene heterocyclic alkylene, hydrocarbylene heterocyclic cycloalkylene, alkynylene heterocyclic alkylene, cycloalkenylene, cycloalkylene alkylene, alkenylene cycloalkenylene, alkenylene, cycloalkenylene alkenylene, alkynylene alkylene heterocyclic alkylene, cycloalkenylene alkylene, alkenylene heterocyclenylene alkylene, alkynylene cycloalkenylene alkenylene, heterocycloalkenylene alkenylene, alkenylene heterocycloalkenylene, alkenylene, heterocycloalkenylene, alkynylene, heterocycloalkenylene, cycloalkenylene, heterocycloalkenylene, cycloalkenylene, cycloalkenyl, One of a hydrocarbylene heterocycloalkenylene, an arylene, a hydrocarbylene arylene, a heteroarylene, a hydrocarbylene heteroarylene, and a hydrocarbylene heteroarylene alkynylene;
c and D may be the same or different;
(3)
wherein,
Q1、Q2、Q3、Q4、Q51and Q6Can be respectively hydrogen atom, alkyl, cycloalkyl, heterocyclic radical, heterocyclic alkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl, aryleneHydrocarbyloxyalkyl, hydrocarbyleneoxycycloalkyl, hydrocarbyleneoxinyl, hydrocarbyleneoxacycloalkyl, hydrocarbyleneoxyalkenyl, hydrocarbyleneoxycycloalkenyl, hydrocarbyleneoxyaryl, cycloalkyleneoxyalkyl, cycloalkyleneoxycycloalkyl, cycloalkyleneoxyalkenyl, cycloalkyleneoxycycloalkenyl, cycloalkyleneoxyalkenyl, cycloalkyleneoxyaryl, one of a heterocycloalkyleneoxyalkyl group, a heterocycloalkyleneoxycycloalkyl group, a heterocycloalkyleneoxetanyl group, a heterocycloalkyleneoxycycloalkyl group, a heterocycloalkyleneoxyalkylene group, a heterocycloalkyleneoxycycloalkenyl group, a heterocycloalkyleneoxoaryl group, an aryloxyalkyl group, an aryloxyalkenyl group, an aryloxyalkyl group, and an aryloxyalkyl group;
Q1、Q22、Q3、Q4、Q5and Q6May be the same or different;
Q5and Q6May or may not be in the same ring structure as the commonly adjacent carbon atom;
Q1and E may or may not be in the same ring structure as the commonly adjacent carbon atom;
Q4and F may or may not be in the same ring structure as the commonly adjacent carbon atom;
e and F may be alkylene, hydrocarbylene heteroalkylene, alkenylene heteroalkenylene, hydrocarbylene heteroalkenylene, alkynylene, cycloalkylene, hydrocarbylene cycloalkylene alkylene, alkenylene cycloalkylene, alkynylene cycloalkylene alkynylene, heterocyclic alkylene, hydrocarbylene heterocyclic alkylene, alkenylene heterocyclic alkylene, hydrocarbylene heterocyclic alkylene, alkynylene heterocyclic alkylene, cycloalkenylene, hydrocarbylene cycloalkenylene alkylene, alkenylene cycloalkenylene, alkenylene, alkynylene cycloalkenylene alkylene, cycloalkylene cycloalkenylene alkylene, alkynylene cycloalkenylene alkylene, alkenylene heterocyclylene alkylene, alkenylene cycloalkenylene, alkynylene cycloalkenylene alkenylene, heterocyclylene alkylene alkenylene, heterocyclylene alkylene heterocyclylene, alkynylene alkylene heterocyclylene alkylene alkenylene cycloalkenylene alkenylene, alkynylene, heterocyclylene alkylene alkenylene cycloalkenylene alkenylene, One of alkenylene heterocycloalkenylene, alkynylene heterocycloalkenylene alkynylene, arylene, hydrocarbylene arylene, alkenylene arylene, hydrocarbylene arylene, alkynylene arylene, heteroarylene, hydrocarbylene heteroarylene, alkenylene heteroarylene, hydrocarbylene heteroarylene, alkynylene heteroarylene, carbonyl, and thiocarbonyl;
e and F may be the same or different;
(4)
wherein,
n is greater than 1;
W1is alkylene, hydrocarbylene heteroalkylene, alkenylene heteroalkenylene, hydrocarbylene heteroalkenylene, alkynylene, cycloalkylene, hydrocarbylene cycloalkylene alkylene, alkenylene cycloalkylene, hydrocarbylene cycloalkylene alkenylene, alkynylene cycloalkylene alkynylene, heterocyclic alkylene, hydrocarbylene heterocyclic alkylene, alkenylene heterocyclic alkylene, hydrocarbylene heterocyclic cycloalkylene, alkynylene heterocyclic alkylene, cycloalkenylene, hydrocarbylene cycloalkenylene alkylene, alkenylene cycloalkenylene, hydrocarbylene cycloalkenylene alkenylene, alkynylene cycloalkenylene, alkynylene, heterocycloalkenylene alkenylene, alkynylene cycloalkenylene alkenylene, heterocycloalkenylene alkenylene, heterocycloalkenylene alkenyleneOne of a group, a hydrocarbylene heterocycloalkenylene group, a alkenylene heterocycloalkenylene group, a hydrocarbylene heterocycloalkenylene group, an alkynylene heterocycloalkenylene alkynylene group, an arylene group, a hydrocarbylene arylene group, an alkenylene arylene group, a hydrocarbylene arylene group, an alkynylene arylene group, a heteroarylene group, a hydrocarbylene heteroarylene group, an alkenylene heteroarylene group, a hydrocarbylene heteroarylene group, a alkynylene heteroarylene group, an alkynylene heteroarylene group, or alkynylene heteroarylene group;
each W2Is one of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, an alkylheteroalkyl group, an alkynyl group, a hydrocarbylene group, a hydrocarbyleneheteroalkylene group, an alkenylene group, a hydrocarbyleneheteroalkylene group, an alkynylene group, or a hydrocarbyleneheteroalkynylene group.
The epoxy resin of the recyclable prepreg, the recyclable cured sheet and the recyclable copper-clad plate is at least one of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin and novolac epoxy resin.
The degradable epoxy resin matrix of the recyclable prepreg, the recyclable cured sheet and the recyclable copper-clad plate also comprises auxiliary materials. The auxiliary material is at least one of an accelerator, a diluent, a toughening agent, a thickening agent, an adhesion promoter, a whitening agent, a pigment, an addition component, a coupling agent, a filler, a thixotropic agent and an antioxidant.
The reinforcing material of the recyclable prepreg, the recyclable curing sheet and the recyclable copper-clad plate is a fiber material or a non-fiber material. The fiber material is at least one of glass fiber, carbon fiber, natural fiber and chemical fiber; the non-fibrous material is at least one of carbon nanotubes, carbon black, metal nanoparticles, organic nanoparticles, iron oxide, and boron nitride.
The applicant provides a recyclable prepreg and a preparation method of the recyclable prepreg, which comprises at least one of a solvent method and a non-solvent method. The solvent method is to prepare a resin prepreg through degradable epoxy resin glue solution containing a solvent. The solvent is acetone, propyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide or xylene.
The non-solvent method is to prepare a resin prepreg through a solvent-free degradable epoxy resin glue solution.
The first method for preparing the recyclable copper-clad plate from the recyclable prepreg and the recyclable curing sheet comprises the following specific preparation steps:
(1) dissolving 45-70 wt% of epoxy resin and 5-25 wt% of degradable curing agent in a solvent, uniformly mixing, adding 15-30 wt% of auxiliary material, and mixing to prepare a degradable epoxy resin glue solution with a solid content of 45-80%;
(2) coating the degradable epoxy resin glue solution on a reinforcing material, and baking for 200-800 sec at 150-200 ℃ to obtain a prepreg;
(3) and (3) orderly overlapping at least 1 prepreg, placing the two sides covered with copper foils into a hot press, and carrying out hot pressing and curing for 60-120 min under the conditions of 2-6 Mpa pressure and 150-200 ℃ to obtain the recyclable copper-clad plate.
The second method for preparing the recyclable copper-clad plate from the recyclable prepreg and the recyclable curing sheet comprises the following specific preparation steps:
(1) melting and uniformly mixing 45-70 wt% of epoxy resin at 60-120 ℃, adding 5-25 wt% of degradable curing agent at 60-100 ℃, uniformly mixing, adding 15-30 wt% of auxiliary material, and mixing to prepare a degradable epoxy resin adhesive;
(2) coating the degradable epoxy resin adhesive on a reinforcing material at the temperature of 60-100 ℃, and baking for about 200-800 sec at the temperature of 150-200 ℃ to obtain a prepreg;
(3) and (3) orderly overlapping at least 1 prepreg, placing the two sides covered with copper foils into a hot press, and carrying out hot pressing and curing for 60-120 min under the conditions of 2-6 Mpa pressure and 150-200 ℃ to obtain the recyclable copper-clad plate.
The invention also provides a method for recovering the recoverable prepreg, the recoverable solidified sheet and the recoverable copper-clad plate, which comprises a step of degrading the degradable epoxy resin matrix by using acid and a solvent.
The degradation is carried out under heating.
The acid is at least one of hydrochloric acid, hydrobromic acid, hydrofluoric acid, acetic acid, trifluoroacetic acid, lactic acid, formic acid, propionic acid, citric acid, methanesulfonic acid, p-toluenesulfonic acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, perchloric acid, benzoic acid, salicylic acid and phthalic acid.
The solvent is at least one of methanol, ethanol, glycol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, nonanol, benzyl alcohol, phenethyl alcohol, p-dimethylolbenzene, m-dimethylolbenzene, o-dimethylolbenzene, p-dihydroxyethylbenzene, m-dihydroxyethylbenzene, o-dihydroxyethylbenzene, water, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, methyltetrahydrofuran, glycerol, dioxane.
The concentration of the acid is 0.1-90 wt%. Preferably, the concentration of the acid is 10 to 20 wt%.
The heating temperature is 15-400 ℃, and the heating time is 1-120 hours. Preferably, the heating temperature is 80-120 ℃, and the heating time is 4-8 hours.
The recovery process further comprises a step of recovering the degradation products by neutralization, filtration and/or precipitation.
The degradable epoxy resin matrix, namely the curing agent and epoxy resin system, can also comprise auxiliary materials, and the degradable cross-linked polymer generated by polymerization can be combined with glass fiber cloth, glass fiber paper, paper and synthetic fiber to prepare the recyclable copper-clad plate.
The copper-clad plate of the invention has the following recovery principle: the copper clad laminate with copper foil stripped is soaked in a hot acid and solvent recovery solution, firstly, an epoxy resin matrix is decomposed, then, a recovery reinforcing material is separated, and finally, a product of epoxy resin degradation is recovered through neutralization of alkali liquor. Under such conditions, the epoxy resin matrix can be decomposed because its crosslinked structure is acid-sensitive, in which acetal groups can undergo bond cleavage, resulting in decomposition of the crosslinked structure of the epoxy resin matrix into a non-crosslinked polymer (e.g., a thermoplastic epoxy resin) that can be dissolved in an organic solvent. When the epoxy resin matrix is fully dissolved, the reinforcing material can be taken out of the solution, and the solution is neutralized by alkali, settled and subjected to solid-liquid separation to recover the epoxy resin matrix degradation product. Both the recycled reinforcement material and the non-crosslinked polymer can be separated, recycled and reused.
The beneficial technical effects of the invention are as follows:
the invention takes the degradable epoxy resin matrix as the raw material to prepare the recyclable copper-clad plate, and can be applied to the preparation of printed circuit boards. Under certain conditions, the printed circuit board can be recycled, and the precious metal, the reinforcing material and the epoxy resin matrix degradation product can be separated and recycled.
The present invention prepares copper clad laminate with degradable epoxy resin matrix and uses it in printed circuit board, and can degrade under mild condition without special condition, and the copper foil, plastic component and reinforcing material in the printed circuit board can be recovered, so that the recovery is more efficient.
The manufacturing process flow of the PCB needs to go through the processes of chemical etching (acidity and alkalinity) and the like, and the copper-clad plate prepared by the invention is degraded under the acidic condition, but is not degraded in the chemical etching (acidity and alkalinity) process of the PCB; in addition, the degradation recovery method can be carried out under relatively mild reaction conditions, is economical and easy to control, and both the reinforcing material and the epoxy resin matrix degradation product can be separated and recovered.
The epoxy resin condensate (namely the degradable cross-linked polymer generated by polymerizing the degradable curing agent and the epoxy resin system) can be degraded to form the thermoplastic epoxy resin polymer, only a small amount of acetal groups are lost in the degradation process, the quality recovery rate of the thermoplastic epoxy resin polymer is high, and the polymer can be processed and used in industrial application.
The mass recovery rate of the epoxy resin condensate and the reinforcing material is more than 96 percent; more than 95% of the reinforced materials (such as glass fiber) in the circuit board composite material can be recovered, the recovered reinforced materials keep most of the original texture and mechanical properties, are stable under the acidic recovery condition, have clean surfaces and basically have no defects, and can be reused in new composite materials; the recovered epoxy resin polymer degradation products can be processed for use on plastic articles.
Drawings
FIG. 1 is a schematic diagram of a partially degraded recyclable copper clad laminate as performed in example 19;
FIG. 2 is a schematic diagram of a 4-layer PCB sample prepared in example 22.
Detailed Description
Example 1: preparation of degradable bromine-containing flame-retardant FR-4 copper-clad plate sample
(1) Preparation of curing agent A:
dissolving 13.4 g of p-benzaldehyde in 370 g of ethanol, weighing 20g of ethanol, putting into a reaction bottle, adding 14.7 g of 85% hydrazine hydrate, stirring, dropwise adding the ethanol solution of p-benzaldehyde in a room-temperature water bath for about 1 hour, and reacting at room temperature for 5-6 hours after dropwise adding. After the reaction, the mixture was filtered, and the filter cake was washed with ethanol and dried to obtain 13.9 g of a yellow solid.
The melting point is 158-166 DEG C
1H-NMR(400MHz,d6-DMSO):7.67(s,2H),7.42(s,4H),6.76(s,4H)。
(2) Preparing degradable epoxy resin glue solution: weighing 40g of bisphenol A type liquid epoxy resin E54(EEW 0.53-0.54 eq./100g), 28g of bisphenol A type solid epoxy resin E21(EEW 0.20-0.22 eq./100g), 132g of low-bromine epoxy resin (Br content is about 20%, EEW 0.23-0.24 eq./100g) and 23.62g A curing agent (AEW2.47N-H eq./100g), adding a proper amount of DMF as a solvent, and dissolving and mixing uniformly; then 0.75g of the silane coupling agent KH560 and 74.5g of molten SiO were added2Micro powder (D505-10 μm), and stirring for 30min by using a high-speed dispersion machine to obtain a glue solution with the solid content S/C of about 60%; gel time S/G of gel liquid at 171 ℃: 300-350 sec.
(3) Preparation of resin prepreg: soaking 7628 glass cloth in the prepared glue solution, baking for 10min at 150 ℃ in an oven to obtain a prepreg with the glue content R/C being about 45%, wherein the gel time P/G of the prepreg glue powder at 171 ℃ is as follows: 150-170 sec.
(4) Preparing a copper-clad plate: and (3) overlapping more than 5 prepared resin prepregs, covering copper foils (1OzHTE copper foils) on two sides, pressing for 60min at 170 ℃ in a hot press, and naturally cooling to obtain the copper-clad plate with the thickness of about 1.0 mm. The performance test method of the copper-clad plate is shown in table 1, and the main performance of the copper-clad plate obtained in the embodiment is shown in table 2. In the table, all the properties of copper-clad plate samples meet the requirements of IPC4101/126, and the use requirements of common FR-4 copper-clad plates are met.
Example 2: preparation of degradable bromine-containing flame-retardant FR-4 copper-clad plate sample
(1) Preparation of curing agent B:
the first step is as follows: sequentially putting 800 g of 2-chloroethanol, 164 g of paraformaldehyde, 4.8 g of p-toluenesulfonic acid and 346 g of toluene into a 2L reaction bottle, heating, refluxing and water dividing for 6h, recovering the toluene under reduced pressure after the reaction is finished, distilling the residue under reduced pressure, and collecting fractions at 71-72 ℃/70Pa to obtain about 739 g of bis (2-chloroethoxy) methane.
The second step is that: putting 2200 g of DMF into a 10L reaction bottle, adding 569 g of bis (2-chloroethoxy) methane, 1000 g of methyl paraben and 300 g of caustic soda flakes in turn under stirring, heating and refluxing for 16 hours, cooling to 60 ℃ after the reaction is finished, concentrating and recovering DMF, adding water into residues to separate out white solid, and drying to obtain 960 g of intermediate.
The third step: 3600 g of ethanol, 960 g of the second-step intermediate and 900 g of 85% hydrazine hydrate are sequentially put into a 10L reaction bottle, the temperature is raised, the mixture is stirred and refluxed for 16 hours, after the reaction is finished, crystals are separated out by cooling, the crystals are filtered, and the solids are recrystallized by ethanol to obtain 389 g of curing agent B.
1H-NMR(400MHz,d6-DMSO):9.63(s,2H),7.79(d,4H),6.98(d,4H),4.76(s,2H),4.45(s,4H),4.17(t,4H),3.84(t,4H)；
LC/MS(M+H+):405。
(2) Preparing degradable epoxy resin glue solution: weighing 40g of bisphenol A type liquid epoxy resin E54(EEW 0.53-0.54 eq./100g), 28g of bisphenol A type solid epoxy resin E21(EEW 0.20-0.22 eq./100g), 132g of low bromine epoxy resin (Br content about 20%, EEW 0.23-0.24 eq./100g) and 58.92g B curing agent (AEW0.99N-H eq./100g), and adding a proper amount ofMethyl ethyl ketone is used as a solvent, and the methyl ethyl ketone and the solvent are dissolved and mixed uniformly; then 0.86g of the silane coupling agent KH560 and 86.3g of molten SiO were added2Micro powder (D505-10 μm), and stirring for 30min by using a high-speed dispersion machine to obtain a glue solution with the solid content S/C of about 60%; gel time S/G of gel liquid at 171 ℃: 280-320 sec.
(3) Preparation of resin prepreg: soaking 7628 glass cloth in the prepared glue solution, baking for 10min at 150 ℃ in an oven to obtain a prepreg with the glue content R/C being about 45%, wherein the gel time P/G of the prepreg glue powder at 171 ℃ is as follows: 140-160 sec.
(4) Preparing a copper-clad plate: and (3) overlapping more than 5 prepared resin prepregs, covering copper foils (1OzHTE copper foils) on two sides, pressing for 60min at 170 ℃ in a hot press, and naturally cooling to obtain the copper-clad plate with the thickness of about 1.0 mm. The performance test method of the copper-clad plate is shown in table 1, and the main performance of the copper-clad plate obtained in the embodiment is shown in table 2. In the table, all the performances of the copper-clad plate all meet the requirements of IPC4101/126, and the use requirements of the common FR-4 copper-clad plate are met.
Example 3: preparation of degradable bromine-containing flame-retardant FR-4 copper-clad plate sample
(1) Preparation of curing agent C:
in a 250 ml three-neck round bottom flask equipped with a condenser, 10g of methyl p-hydroxybenzoate, 6.8 g of dibromomethane and 3.9 g of sodium hydroxide are dissolved in 25 ml of N, N-Dimethylformamide (DMF), the mixture is heated and refluxed for 5 hours, then cooled to room temperature, the mother liquor is concentrated, water is added to separate out a solid, and the solid is filtered and dried to obtain 3g of an intermediate.
Dissolving the intermediate in 10 ml ethanol in a 250 ml three-neck round-bottom flask with a condenser, adding 1.4 g hydrazine hydrate, heating to 78 deg.C, refluxing for 2 hr, cooling to below 5 deg.C, separating out solid, suction filtering the separated out solid, and washing with ethanol to obtain 1.5 g white solid product.
Melting point: 248-249 deg.C
1H-NMR(400MHz,d6-DMSO):9.66(s,2H),7.81(d,4H),7.14(d,4H),5.96(s,2H),4.45(s,4H)；
LC/MS(M+H+):317。
(2) Preparing degradable epoxy resin glue solution: weighing 40g of bisphenol A type liquid epoxy resin E54(EEW 0.53-0.54 eq./100g), 28g of bisphenol A type solid epoxy resin E21(EEW 0.20-0.22 eq./100g), 132g of low-bromine epoxy resin (Br content is about 20%, EEW 0.23-0.24 eq./100g) and 46.15g C curing agent (AEW1.26N-H eq./100g), adding a proper amount of N-methylpyrrolidone as a solvent, and dissolving and mixing uniformly; then 0.82g of silane coupling agent KH560 and 82.0g of molten SiO were added2Micro powder (D505-10 mu m), adding 4.92g of UR-200 curing accelerator, and stirring for 30min by using a high-speed dispersion machine to obtain a glue solution with the solid content S/C being about 60%; gel time S/G of gel liquid at 171 ℃: 260-300 sec.
(3) Preparation of resin prepreg: soaking 7628 glass cloth in the prepared glue solution, baking for 10min at 150 ℃ in an oven to obtain a prepreg with the glue content R/C being about 45%, wherein the gel time P/G of the prepreg glue powder at 171 ℃ is as follows: 130-150 sec.
(4) Preparing a copper-clad plate: and (3) overlapping more than 5 prepared resin prepregs, covering copper foils (1OzHTE copper foils) on two sides, pressing for 60min at 170 ℃ in a hot press, and naturally cooling to obtain the copper-clad plate with the thickness of about 1.0 mm. The performance test method of the copper-clad plate is shown in table 1, and the main performance of the copper-clad plate obtained in the embodiment is shown in table 2. In the table, all the performances of the copper-clad plate all meet the requirements of IPC4101/126, and the use requirements of the common FR-4 copper-clad plate are met.
Example 4: preparation of degradable bromine-containing flame-retardant FR-4 copper-clad plate sample
(1) Can be used forPreparing a degraded epoxy resin glue solution: weighing 40g of bisphenol A type liquid epoxy resin E54(EEW 0.53-0.54 eq./100g), 10g of trifunctional epoxy resin XY636(EEW 0.69-0.71 eq./100g), 70g of low-bromine epoxy resin (Br content is about 20%, EEW 0.23-0.24 eq./100g), 80g of isocyanate modified epoxy (EEW 0.34-0.40 eq./100g) and 46.15g B curing agent (AEW0.99N-H eq./100g), adding a proper amount of acetone as a solvent, and dissolving and mixing uniformly; then 0.92g of the silane coupling agent KH560 and 91.7g of molten SiO were added2Micro powder (D505-10 mu m), adding 33g of tetrabromobisphenol A serving as a flame retardant, and stirring for 30min by using a high-speed dispersion machine to prepare a glue solution with the solid content S/C being about 60%; gel time S/G of gel liquid at 171 ℃: 280-320 sec.
(2) Preparation of resin prepreg: soaking 7628 glass cloth in the prepared glue solution, baking for 10min at 150 ℃ in an oven to obtain a prepreg with the glue content R/C being about 45%, wherein the gel time P/G of the prepreg glue powder at 171 ℃ is as follows: 140-160 sec.
(3) Preparing a copper-clad plate: and (3) overlapping more than 5 prepared resin prepregs, covering copper foils (1OzHTE copper foils) on two sides, pressing for 60min at 190 ℃ in a hot press, and naturally cooling to obtain the copper-clad plate with the thickness of about 1.0 mm. The performance test method of the copper-clad plate is shown in table 1, and the main performance of the copper-clad plate obtained in the embodiment is shown in table 2. In the table, all the performances of the copper-clad plate meet the requirements of IPC4101/128 and meet the use requirements of a Hi-Tg FR-4 copper-clad plate.
Example 5: preparation of degradable bromine-containing flame-retardant FR-4 copper-clad plate sample
(1) Preparing degradable epoxy resin glue solution: weighing 40g of bisphenol A type liquid epoxy resin E54(EEW 0.53-0.54 eq./100g), 10g of trifunctional epoxy resin XY636(EEW 0.69-0.71 eq./100g), 70g of low-bromine epoxy resin (Br content is about 20%, EEW 0.23-0.24 eq./100g), 80g of isocyanate modified epoxy (EEW 0.34-0.40 eq./100g) and 58.9g C curing agent (AEW1.26N-H eq./100g), adding a proper amount of DMF as a solvent, and dissolving and mixing uniformly; then 0.86g of a silane coupling agent KH560 and86.3g of fused SiO2Micro powder (D505-10 mu m), adding 31g of tetrabromobisphenol A serving as a flame retardant and 5.17g of UR-200 curing agent, and stirring for 30min by adopting a high-speed dispersion machine to prepare a glue solution with the solid content S/C being about 60%; gel time S/G of gel liquid at 171 ℃: 300-340 sec.
(2) Preparation of resin prepreg: soaking 7628 glass cloth in the prepared glue solution, baking for 10min at 150 ℃ in an oven to obtain a prepreg with the glue content R/C being about 45%, wherein the gel time P/G of the prepreg glue powder at 171 ℃ is as follows: 150-170 sec.
(3) Preparing a copper-clad plate: and (3) overlapping more than 5 prepared resin prepregs, covering copper foils (1OzHTE copper foils) on two sides, pressing for 60min at 190 ℃ in a hot press, and naturally cooling to obtain the copper-clad plate with the thickness of about 1.0 mm. The performance test method of the copper-clad plate is shown in table 1, and the main performance of the copper-clad plate obtained in the embodiment is shown in table 2. In the table, all the performances of the copper-clad plate meet the requirements of IPC4101/128 and meet the use requirements of a Hi-Tg FR-4 copper-clad plate.
Example 6: preparation of degradable halogen-free flame-retardant FR-4 copper-clad plate sample
(1) Preparing degradable epoxy resin glue solution: weighing 70g of bisphenol A type liquid epoxy resin E54(EEW 0.53-0.54 eq./100g), 50g of bisphenol A type solid epoxy resin E21(EEW 0.20-0.22 eq./100g), 80g of phosphorus-containing epoxy resin (P content is 2.5%, EEW 0.22-0.24 eq./100g) and 26.78g A curing agent (AEW2.47N-H eq./100g), adding a proper amount of xylene as a solvent, and dissolving and mixing uniformly; then 0.76g of silane coupling agent KH560 and 75.6g of molten SiO were added2Micro powder (D505-10 μm), and stirring for 30min by using a high-speed dispersion machine to obtain a glue solution with the solid content S/C of about 60%; gel time S/G of gel liquid at 171 ℃: 300-340 sec.
(2) Preparation of resin prepreg: soaking 7628 glass cloth in the prepared glue solution, baking for 10min at 150 ℃ in an oven to obtain a prepreg with the glue content R/C being about 45%, wherein the gel time P/G of the prepreg glue powder at 171 ℃ is as follows: 150-170 sec.
(3) Preparing a copper-clad plate: and (3) overlapping more than 5 prepared resin prepregs, covering copper foils (1OzHTE copper foils) on two sides, pressing for 60min at 170 ℃ in a hot press, and naturally cooling to obtain the copper-clad plate with the thickness of about 1.0 mm. The performance test method of the copper-clad plate is shown in table 1, and the main performance of the copper-clad plate obtained in the embodiment is shown in table 3. In the table, all the performances of the copper-clad plate meet the requirements of IPC4101/126, and the use requirements of the halogen-free flame-retardant FR-4 copper-clad plate are met.
Example 7: preparation of degradable halogen-free flame-retardant FR-4 copper-clad plate sample
(1) Preparing degradable epoxy resin glue solution: weighing 20g of bisphenol A type liquid epoxy resin E54(EEW 0.53-0.54 eq./100g), 10g of trifunctional epoxy resin XY636(EEW 0.69-0.71 eq./100g), 80g of isocyanate modified epoxy (EEW 0.34-0.40 eq./100g), 90g of phosphorus-containing epoxy resin (P content is 2%, EEW 0.37-0.42 eq./100g) and 83.4g B curing agent (AEW0.99N-H eq./100g), adding a proper amount of toluene as a solvent, and dissolving and mixing uniformly; then 0.94g of silane coupling agent KH560 and 94.4g of molten SiO were added2Adding 22.6g of SPB-100 phosphazene flame retardant into the micro powder (D505-10 mu m), and stirring for 30min by using a high-speed dispersion machine to obtain a glue solution with the solid content S/C of about 60%; gel time S/G of gel liquid at 171 ℃: 260-300 sec.
(2) Preparation of resin prepreg: soaking 7628 glass cloth in the prepared glue solution, baking for 10min at 150 ℃ in an oven to obtain a prepreg with the glue content R/C being about 45%, wherein the gel time P/G of the prepreg glue powder at 171 ℃ is as follows: 130-150 sec.
(3) Preparing a copper-clad plate: and (3) overlapping more than 5 prepared resin prepregs, covering copper foils (1OzHTE copper foils) on two sides, pressing for 60min at 190 ℃ in a hot press, and naturally cooling to obtain the copper-clad plate with the thickness of about 1.0 mm. The performance test method of the copper-clad plate is shown in table 1, and the main performance of the copper-clad plate obtained in the embodiment is shown in table 3. In the table, all the performances of the copper-clad plate meet the requirements of IPC4101/128, and the use requirements of the halogen-free flame-retardant FR-4 copper-clad plate are met.
Example 8: preparation of degradable halogen-free flame-retardant FR-4 copper-clad plate sample
(1) Preparing degradable epoxy resin glue solution: weighing 20g of bisphenol A type liquid epoxy resin E54(EEW 0.53-0.54 eq./100g), 10g of trifunctional epoxy resin XY636(EEW 0.69-0.71 eq./100g), 80g of isocyanate modified epoxy (EEW 0.34-0.40 eq./100g), 90g of phosphorus-containing epoxy resin (P content is 2%, EEW 0.37-0.42 eq./100g) and 65.3g C curing agent (AEW1.26N-H eq./100g), adding a proper amount of methyl ethyl ketone as a solvent, and dissolving and mixing uniformly; then 0.88g of silane coupling agent KH560 and 88.4g of molten SiO were added2Adding 21.6g of SPB-100 phosphazene flame retardant and 5.30gUR-200 curing accelerator into micro powder (D505-10 mu m), and stirring for 30min by using a high-speed dispersion machine to obtain a glue solution with the solid content S/C being about 60%; gel time S/G of gel liquid at 171 ℃: 280-320 sec.
(2) Preparation of resin prepreg: soaking 7628 glass cloth in the prepared glue solution, baking for 10min at 150 ℃ in an oven to obtain a prepreg with the glue content R/C being about 45%, wherein the gel time P/G of the prepreg glue powder at 171 ℃ is as follows: 140-160 sec.
(3) Preparing a copper-clad plate: and (3) overlapping more than 5 prepared resin prepregs, covering copper foils (1OzHTE copper foils) on two sides, pressing for 60min at 190 ℃ in a hot press, and naturally cooling to obtain the copper-clad plate with the thickness of about 1.0 mm. The performance test method of the copper-clad plate is shown in table 1, and the main performance of the copper-clad plate obtained in the embodiment is shown in table 3. In the table, all the performances of the copper-clad plate meet the requirements of IPC4101/128, and the use requirements of the halogen-free flame-retardant FR-4 copper-clad plate are met.
Example 9: preparation of degradable halogen-free flame-retardant FR-4 copper-clad plate sample
(1) Preparing degradable epoxy resin glue solution: 40g of bisphenol A type liquid epoxy resin E54 (E)0.53-0.54 eq./100g of EW), 80g of isocyanate modified epoxy (EEW 0.34-0.40 eq./100g), 80g of phosphorus-containing epoxy resin (P content is 2.5%, EEW 0.22-0.24 eq./100g), 69.9g B curing agent (AEW0.99N-H eq./100g), adding a proper amount of DMF as a solvent, and dissolving and mixing uniformly; then 0.90g of silane coupling agent KH560 and 90.0g of molten SiO were added2Micro powder (D505-10 μm), and stirring for 30min by using a high-speed dispersion machine to obtain a glue solution with the solid content S/C of about 60%; gel time S/G of gel liquid at 171 ℃: 300-340 sec.
(2) Preparation of resin prepreg: soaking 7628 glass cloth in the prepared glue solution, baking for 10min at 150 ℃ in an oven to obtain a prepreg with the glue content R/C being about 45%, wherein the gel time P/G of the prepreg glue powder at 171 ℃ is as follows: 150-170 sec.
(3) Preparing a copper-clad plate: and (3) overlapping more than 5 prepared resin prepregs, covering copper foils (1OzHTE copper foils) on two sides, pressing for 60min at 180 ℃ in a hot press, and naturally cooling to obtain the copper-clad plate with the thickness of about 1.0 mm. The performance test method of the copper-clad plate is shown in table 1, and the main performance of the copper-clad plate obtained in the embodiment is shown in table 3. In the table, all the performances of the copper-clad plate meet the requirements of IPC4101/128, and the use requirements of the halogen-free flame-retardant FR-4 copper-clad plate are met.
Example 10: preparation of degradable halogen-free flame-retardant FR-4 copper-clad plate sample
(1) Preparing degradable epoxy resin glue solution: weighing 40g of bisphenol A type liquid epoxy resin E54(EEW 0.53-0.54 eq./100g), 80g of isocyanate modified epoxy (EEW 0.34-0.40 eq./100g), 80g of phosphorus-containing epoxy resin (P content is 2.5%, EEW 0.22-0.24 eq./100g), 54.7g C curing agent (AEW1.26N-H eq./100g), 20g of trimethylolpropane triglycidyl ether (EEW 0.68-0.74 eq./100g), and heating at 70 ℃ for uniform mixing; then 0.85g of silane coupling agent KH560 and 84.9g of molten SiO were added2Micro powder (D505-10 mu m), then adding 5.09g of UR-200 curing accelerator, and stirring for 30min by adopting a high-speed dispersion machine to prepare glue solution; gel time S/G of gel liquid at 171 ℃: 280-320 sec.
(2) Preparation of resin prepreg: soaking 7628 glass cloth in the prepared glue solution at 70 ℃, then baking for 10min in an oven at 150 ℃ to obtain a prepreg with the glue content R/C being about 45%, wherein the gel time P/G of the prepreg glue powder at 171 ℃ is as follows: 140-160 sec.
(3) Preparing a copper-clad plate: and (3) overlapping more than 5 prepared resin prepregs, covering copper foils (1OzHTE copper foils) on two sides, pressing for 60min at 180 ℃ in a hot press, and naturally cooling to obtain the copper-clad plate with the thickness of about 1.0 mm. The performance test method of the copper-clad plate is shown in table 1, and the main performance of the copper-clad plate obtained in the embodiment is shown in table 3. In the table, all the performances of the copper-clad plate meet the requirements of IPC4101/128, and the use requirements of the halogen-free flame-retardant FR-4 copper-clad plate are met.
TABLE 1
TABLE 2
TABLE 3
Example 11: preparation of glass fiber curing sheet
(1) Preparing degradable epoxy resin glue solution: 40g of bisphenol A type liquid epoxy resin E54(EEW 0.53-0.54 eq./100g) and 80g of isocyanate modified epoxy (EEW)0.34 to 0.40 eq/100 g), 80g of phosphorus-containing epoxy resin (the P content is 2.5 percent, EEW is 0.22 to 0.24 eq/100 g), 54.7g C curing agent (AEW1.26N-H eq/100 g), adding a proper amount of DMF as a solvent, and dissolving and mixing uniformly; then 0.85g of silane coupling agent KH560 and 84.9g of molten SiO were added2Micro powder (D505-10 mu m), adding 5.09g of UR-200 curing accelerator, and stirring for 30min by a high-speed dispersion machine to obtain a glue solution with the solid content S/C being about 60%; gel time S/G of gel liquid at 171 ℃: 280-320 sec.
(2) Preparation of resin prepreg: soaking 7628 glass cloth in the prepared glue solution, baking for 10min at 150 ℃ in an oven to obtain a prepreg with the glue content R/C being about 45%, wherein the gel time P/G of the prepreg glue powder at 171 ℃ is as follows: 140-160 sec.
(3) Preparing a glass fiber curing sheet: and (3) overlapping more than 5 prepared resin prepregs, pressing for 60min at 180 ℃ in a hot press, and naturally cooling to obtain the glass fiber solidified sheet.
Example 12: degradation of copper clad laminate
Adding 1g of the copper-clad plate sample in the embodiment 1, 5 ml of concentrated hydrochloric acid and 95 ml of ethylene glycol into a 250 ml three-neck flask, stirring and heating to 160 ℃, cooling to 100 ℃ after 6 hours, filtering while hot, separating the copper foil and the glass fiber from the degradation solution, neutralizing the degradation solution with 5% of sodium hydroxide solution, separating out a solid, filtering, washing the solid with water, and drying to obtain 0.96 g of thermosetting epoxy resin degradation product, copper foil and glass fiber, wherein the mass recovery rate is 96%.
Example 13: degradation of copper clad laminate
Adding 1g of the copper-clad plate sample in the embodiment 1, 10 ml of concentrated hydrochloric acid and 90 ml of ethylene glycol into a 250 ml three-neck flask, stirring and heating to 160 ℃, cooling to 100 ℃ after 6 hours, filtering while hot, separating the copper foil and the glass fiber from the degradation solution, neutralizing the degradation solution with 10% of sodium hydroxide solution, separating out a solid, filtering, washing the solid with water, and drying to obtain 0.95 g of thermosetting epoxy resin degradation product, copper foil and glass fiber, wherein the mass recovery rate is 95%.
Example 14: degradation of copper clad laminate
Adding 1g of the copper-clad plate sample in the embodiment 2, 5 ml of concentrated hydrochloric acid and 95 ml of ethylene glycol into a 250 ml three-neck flask, stirring and heating to 140 ℃, cooling to 100 ℃ after 4 hours, filtering while hot, separating the copper foil and the glass fiber from the degradation solution, neutralizing the degradation solution with 5% of sodium hydroxide solution, separating out a solid, filtering, washing the solid with water, and drying to obtain 0.95 g of thermosetting epoxy resin degradation product, copper foil and glass fiber, wherein the mass recovery rate is 95%.
Example 15: degradation of copper clad laminate
Adding 1g of the copper-clad plate sample in the embodiment 2, 5 ml of concentrated hydrochloric acid and 95 ml of octanol into a 250 ml three-neck flask, stirring and heating to 155 ℃, cooling to 100 ℃ after 4 hours, filtering while hot, separating the copper foil and the glass fiber from the degradation solution, neutralizing the degradation solution with 5% of sodium hydroxide solution, separating out a solid, filtering, washing the solid with water, and drying to obtain 0.96 g of thermosetting epoxy resin degradation product, copper foil and glass fiber, wherein the mass recovery rate is 96%.
Example 16: degradation of copper clad laminate
Adding 1g of the copper-clad plate sample in the embodiment 3, 5 ml of concentrated hydrochloric acid and 95 ml of heptanol into a 250 ml three-neck flask, stirring and heating to 155 ℃, cooling to 100 ℃ after 4 hours, filtering while hot, separating the copper foil and the glass fiber from the degradation solution, neutralizing the degradation solution with 20% of sodium hydroxide solution, separating out a solid, filtering, washing the solid with water, and drying to obtain 0.95 g of thermosetting epoxy resin degradation product, copper foil and glass fiber, wherein the mass recovery rate is 95%.
Example 17: degradation of copper clad laminate
Adding 1g of the copper-clad plate sample in the embodiment 3, 5 ml of concentrated hydrochloric acid and 95 ml of ethylene glycol into a 250 ml three-neck flask, stirring and heating to 160 ℃, cooling to 100 ℃ after 4 hours, filtering while hot, separating the copper foil and the glass fiber from the degradation solution, neutralizing the degradation solution with 20% of sodium hydroxide solution, separating out a solid, filtering, washing the solid with water, and drying to obtain 0.95 g of thermosetting epoxy resin degradation product, copper foil and glass fiber, wherein the mass recovery rate is 95%.
Example 18: degradation of glass fiber cured sheet
In a 250 ml three-neck flask, 1g of the glass fiber solidified sheet in the example 11, 5 ml of concentrated hydrochloric acid and 95 ml of ethylene glycol are added, stirred and heated to 160 ℃, cooled to 100 ℃ after 3 hours, filtered while hot, the glass fiber is separated from the degradation solution, the degradation solution is neutralized by 20% sodium hydroxide solution, solid is separated out, filtered, washed by water and dried to obtain 0.95 g of thermosetting epoxy resin degradation product and glass fiber, and the mass recovery rate is 95%.
Example 19: demonstration of degradation of copper-clad plate
The copper clad laminate sample strip of example 3, 10 ml of concentrated hydrochloric acid and 90 ml of ethylene glycol were added to a 500 ml beaker, stirred and heated to 145 ℃ and after 1 hour the copper foil was partially separated, and a white glass fiber cloth was seen, see the partial degradation schematic diagram shown in fig. 1.
Example 20: copper-clad plate sample acid etching
(1) The copper-clad plate sample test strip in the example 9 and 100 ml of acid copper chloride etching solution are added into a 500 ml beaker, the temperature is heated to 50 ℃, the copper foil is completely etched after 5min, and the copper-clad plate substrate is found to be smooth and flat without copper scrap residue after the sample is washed and dried by clean water.
Example 21: copper-clad plate sample alkaline etching
The copper-clad plate sample test strip in the example 9 and 100 ml of alkaline copper chloride etching solution are added into a 500 ml beaker, the temperature is heated to 50 ℃, the copper foil is completely coated after 5min, and after the sample is washed by clean water and dried, the copper-clad plate substrate is smooth and flat and has no copper scrap residue.
Example 22: 4-layer PCB (printed Circuit Board) circuit board sample manufacturing method
(1) Example 9 the degradable epoxy resin glue solution prepared in step (1) is impregnated into 7628 glass cloth, and then baked in an oven phase at 150 ℃ for 10min to prepare a prepreg with a glue content R/C of about 43%, wherein the gel time P/G of the prepreg glue solution at 171 ℃ is as follows: 150-170 sec.
(2) And (2) overlapping 7 semi-cured films prepared in the step (1), covering copper foils (1Oz HTE copper foils) on two sides, pressing for 60min at 180 ℃ in a hot press, and naturally cooling to obtain the copper-clad plate with the thickness of about 1.3 mm.
(3) Example 9 the degradable epoxy resin glue solution prepared in step (1) is impregnated into 1080 glass cloth, and then baked in an oven phase at 150 ℃ for 10min to prepare a prepreg with a glue content R/C of about 64%, wherein the gel time P/G of the prepreg glue solution at 171 ℃ is as follows: 150-170 sec.
(4) Cutting the copper-clad plate sample prepared in the step (2) and the semi-cured film prepared in the step (3) into a size of 416mm by 518mm, and sending the cut sample to a PCB (printed circuit board) production line to be processed into a four-layer PCB, wherein the specific processing steps are as follows by combining the steps shown in figure 2:
(a) preparing an inner layer circuit pattern from a cut copper-clad plate sample by adopting an inner layer dry film method through a plurality of processes such as inner layer film pasting, exposure and development, inner layer etching (acid etching process) and film stripping;
(b) performing brown oxidation treatment on the sample plate of the prepared graphic circuit, then taking a prepreg and a copper foil to be overlapped according to a lower overlapping structure, and after overlapping, sending the prepreg and the copper foil to a vacuum press for hot pressing for 60min under the conditions of 2.5Mpa and 180 ℃ to obtain a 4-layer plate with the thickness of 1.5 mm;
(c) mechanically drilling a 4-layer plate sample, oxidizing an epoxy cured substance by potassium permanganate in a NaOH solution to remove residual dirt in the drilled hole to enable the hole wall to be smooth and tidy, and then plating copper to enable the through hole to be metallized;
(d) carrying out pattern electroplating on the 4-layer plate by adopting a normal outer layer dry film, electroplating copper and tin, then carrying out alkaline etching and film stripping, and stripping tin to obtain an outer layer pattern circuit;
(e) and (3) carrying out resistance welding, character milling, appearance milling, testing and chemical tin deposition on the four-layer board sample with the circuit prepared to obtain a 4-layer PCB circuit board sample.
Claims (10)
1. A recoverable copper-clad plate for a printed circuit board is characterized by comprising a copper foil and a recoverable prepreg; the recyclable copper-clad plate is a double-layer plate or a multilayer plate and is prepared by laminating a recyclable prepreg and a copper foil;
the preparation method comprises the following specific steps:
(1) dissolving 45-70 wt% of epoxy resin and 5-25 wt% of degradable curing agent in a solvent, uniformly mixing, adding 15-30 wt% of auxiliary material, and mixing to prepare a degradable epoxy resin glue solution with a solid content of 45-80%;
(2) coating the degradable epoxy resin glue solution on a reinforcing material, and baking for 200-800 sec at 150-200 ℃ to obtain a prepreg;
(3) orderly overlapping at least 1 prepreg, placing copper foils covered on two sides into a hot press, and carrying out hot pressing and curing for 60-120 min under the conditions of 2-6 Mpa pressure and 150-200 ℃ to obtain a recyclable copper-clad plate;
or the specific preparation steps are as follows:
(1) melting and uniformly mixing 45-70 wt% of epoxy resin at 60-120 ℃, adding 5-25 wt% of degradable curing agent at 60-100 ℃, uniformly mixing, adding 15-30 wt% of auxiliary material, and mixing to prepare a degradable epoxy resin adhesive;
(2) coating the degradable epoxy resin adhesive on a reinforcing material at the temperature of 60-100 ℃, and baking for 200-800 sec at the temperature of 150-200 ℃ to obtain a prepreg;
(3) orderly overlapping at least 1 prepreg, placing copper foils covered on two sides into a hot press, and carrying out hot pressing and curing for 60-120 min under the conditions of 2-6 Mpa pressure and 150-200 ℃ to obtain a recyclable copper-clad plate;
the degradable curing agent is one or more of the degradable curing agents with the following molecular structure general formula:
(1)
wherein,
r1 is one of a hydrogen atom, alkyl group, cycloalkyl group, heterocyclic group, heterocycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, heteroaryl group, alkylheteroalkyl group, alkynyl group, hydrocarbylene group, hydrocarbyleneheteroalkylene group, alkenylene group, hydrocarbyleneheteroalkylene group, alkynylene group, or hydrocarbyleneheteroalkylene group;
r2 is one of a hydrogen atom, alkyl group, cycloalkyl group, heterocyclic group, heterocycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, heteroaryl group, alkylheteroalkyl group, alkynyl group, hydrocarbylene group, hydrocarbyleneheteroalkylene group, alkenylene group, hydrocarbyleneheteroalkylene group, alkynylene group, or hydrocarbyleneheteroalkylene group;
r1 and R2 may be the same or different;
r1 and R2 may also be in the same ring structure with the common adjacent carbon atom;
a is one of an arylidene group, a hydrocarbylidene arylidene group, an alkenylidene arylidene group, an alkynylidene arylidene group, a heteroaromatic group, a hydrocarbylidene heteroaromatic group, an alkenylidene heteroaromatic group, and an alkynylidene heteroaromatic group;
b is one of an arylidene group, a hydrocarbylidene arylidene group, an alkenylidene arylidene group, an alkynylidene arylidene group, a heteroaromatic group, a hydrocarbylidene heteroaromatic group, an alkenylidene heteroaromatic group and an alkynylidene heteroaromatic group;
a and B may be the same or different;
r3 is
R4 is
R3 and R4 may be the same or different;
r5 is one of hydrogen atom, alkyl, cycloalkyl, heterocyclic group, heterocyclic alkyl, alkenyl, cycloalkenyl, aryl, heteroaryl, alkoxyalkyl or alkynyl;
r6 is one of hydrogen atom, alkyl, cycloalkyl, heterocyclic group, heterocyclic alkyl, alkenyl, cycloalkenyl, aryl, heteroaryl, alkoxyalkyl or alkynyl;
r5 and R6 may be the same or different;
Xn-is one of C1-C10 aliphatic carboxylate anions, C1-C10 alicyclic carboxylate anions, aromatic carboxylate anions and heterocyclic aromatic carboxylate anions;
n is 1, 2 or 3;
m is 0.1 to 3;
y is one of Lewis acids;
(2)
wherein,
p1 is one of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, an alkylheteroalkyl group, an alkynyl group, a hydrocarbylene group, a hydrocarbyleneheteroalkylene group, an alkenylene group, a hydrocarbyleneheteroalkylene group, an alkynylene group, or a hydrocarbyleneheteroalkynylene group;
p2 is one of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, an alkylheteroalkyl group, an alkynyl group, a hydrocarbylene group, a hydrocarbyleneheteroalkylene group, an alkenylene group, a hydrocarbyleneheteroalkylene group, an alkynylene group, or a hydrocarbyleneheteroalkynylene group;
p1 and P2 may be the same or different;
p1 and P2 may also be in the same ring structure with the common adjacent carbon atom;
c is alkylene, hydrocarbylene heteroalkylene, alkenylene heteroalkenylene, hydrocarbylene heteroalkenylene, alkynylene, cycloalkylene, hydrocarbylene cycloalkylene alkylene, alkenylene cycloalkylene, hydrocarbylene cycloalkylene alkenylene, alkynylene cycloalkylene alkynylene, heterocyclic alkylene, hydrocarbylene heterocyclic alkylene, alkenylene heterocyclic alkylene, hydrocarbylene heterocyclic alkylene, alkynylene heterocyclic alkylene, alkenylene cycloalkylene, cycloalkenylene alkenylene, heterocyclic alkylene, heterocyclylene alkylene, cycloalkylene, heterocyclylene, cycloalkenylene, alkenylene, cycloalkenylene alkenylene, alkenylene, heterocyclylene alkenylene, alkynylene cycloalkenylene, heterocyclylene alkenylene, heterocyclylene alkylene heterocyclylene, heterocyclylene alkylene, cycloalkylene, alkenylene, heterocyclylene, cycloalkylene, cycloalkenylene, cycloalkylene, heterocyclylene, alkynylene, heterocyclylene, cycloalkenylene, cycloalkylene, cycloalkenylene, One of a hydrocarbylene heterocycloalkenylene, an arylene, a hydrocarbylene arylene, a heteroarylene, a hydrocarbylene heteroarylene, and a hydrocarbylene heteroarylene alkynylene;
d is alkylene, hydrocarbylene heteroalkylene, alkenylene heteroalkenylene, hydrocarbylene heteroalkenylene, alkynylene, cycloalkylene, hydrocarbylene cycloalkylene, alkenylene cycloalkylene, hydrocarbylene cycloalkylene alkenylene, alkynylene cycloalkylene alkynylene, heterocyclic alkylene, hydrocarbylene heterocyclic alkylene, alkenylene heterocyclic alkylene, hydrocarbylene heterocyclic cycloalkylene, alkynylene heterocyclic alkylene, cycloalkenylene, cycloalkylene alkylene, alkenylene cycloalkenylene, alkenylene, cycloalkenylene alkenylene, alkynylene alkylene heterocyclic alkylene, cycloalkenylene alkylene, alkenylene heterocyclenylene alkylene, alkynylene cycloalkenylene alkenylene, heterocycloalkenylene alkenylene, alkenylene heterocycloalkenylene, alkenylene, heterocycloalkenylene, alkynylene, heterocycloalkenylene, cycloalkenylene, heterocycloalkenylene, cycloalkenylene, cycloalkenyl, One of a hydrocarbylene heterocycloalkenylene, an arylene, a hydrocarbylene arylene, a heteroarylene, a hydrocarbylene heteroarylene, and a hydrocarbylene heteroarylene alkynylene;
c and D may be the same or different;
(3)
wherein,
Q1、Q2、Q3、Q4、Q51and Q6Which may be respectively a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a hydrocarbyleneoxyalkyl group, a hydrocarbyleneoxycycloalkyl group, a hydrocarbyleneoxyalkylene group, a hydrocarbyleneoxycycloalkenyl group, a hydrocarbyleneoxyaryl group, a,One of alkylene oxide aryl, alkylene oxide alkyl, alkylene oxide cycloalkyl, alkylene oxide heterocyclic group, alkylene oxide cycloalkyl, alkylene oxide alkenyl, alkylene oxide cycloalkenyl, alkylene oxide aryl, alkylene oxide alkyl, alkylene oxide cycloalkyl, alkylene oxide heterocyclic group, alkylene oxide cycloalkyl, alkylene oxide alkenyl, alkylene oxide cycloalkenyl, alkylene oxide heteroaryl, alkylene oxide aryl, alkylene oxide heteroaryl, arylene oxide aryl, arylene oxide alkyl, arylene oxide cycloalkyl, arylene oxide alkenyl, arylene oxide aryl, and arylene oxide aryl;
Q1、Q2、Q3、Q4、Q5and Q6May be the same or different;
Q5and Q6May or may not be in the same ring structure as the commonly adjacent carbon atom;
Q1and E may or may not be in the same ring structure as the commonly adjacent carbon atom;
Q4and F may or may not be in the same ring structure as the commonly adjacent carbon atom;
e and F may be alkylene, hydrocarbylene heteroalkylene, alkenylene heteroalkenylene, hydrocarbylene heteroalkenylene, alkynylene, cycloalkylene, hydrocarbylene cycloalkylene alkylene, alkenylene cycloalkylene, alkynylene cycloalkylene alkynylene, heterocyclic alkylene, hydrocarbylene heterocyclic alkylene, alkenylene heterocyclic alkylene, hydrocarbylene heterocyclic alkylene, alkynylene heterocyclic alkylene, cycloalkenylene, hydrocarbylene cycloalkenylene alkylene, alkenylene cycloalkenylene, alkenylene, alkynylene cycloalkenylene alkylene, cycloalkylene cycloalkenylene alkylene, alkynylene cycloalkenylene alkylene, alkenylene heterocyclylene alkylene, alkenylene cycloalkenylene, alkynylene cycloalkenylene alkenylene, heterocyclylene alkylene alkenylene, heterocyclylene alkylene heterocyclylene, alkynylene alkylene heterocyclylene alkylene alkenylene cycloalkenylene alkenylene, alkynylene, heterocyclylene alkylene alkenylene cycloalkenylene alkenylene, One of alkenylene heterocycloalkenylene, alkynylene heterocycloalkenylene alkynylene, arylene, hydrocarbylene arylene, alkenylene arylene, hydrocarbylene arylene, alkynylene arylene, heteroarylene, hydrocarbylene heteroarylene, alkenylene heteroarylene, hydrocarbylene heteroarylene, alkynylene heteroarylene, carbonyl, and thiocarbonyl;
e and F may be the same or different;
(4)
wherein,
n is greater than 1;
W1is alkylene, hydrocarbylene heteroalkylene, alkenylene heteroalkenylene, hydrocarbylene heteroalkenylene, alkynylene, cycloalkylene, hydrocarbylene cycloalkylene, alkenylene cycloalkylene, hydrocarbylene cycloalkylene alkenylene, alkynylene cycloalkylene alkynylene, heterocyclic alkylene, hydrocarbylene heterocyclic alkylene, alkenylene heterocyclic alkylene, hydrocarbylene heterocyclic alkylene, alkynylene heterocyclic alkylene, cycloalkenylene, hydrocarbylene cycloalkenylene alkylene, alkenylene cycloalkenylene, alkenylene, hydrocarbylene cycloalkenylene alkenylene, alkynylene cycloalkenylene, heterocyclic alkylene, hydrocarbylene heterocycloalkenylene, hydrocarbylene heterocyclic alkylene, alkenylene heterocycloalkenylene, alkenylene, heterocycloalkenylene alkenylene, alkynylene, heterocycloalkenylene, Alkylene heterocycloalkenylene, alkynylene heterocycloalkenylene, arylene, alkenylene arylene, heteroaralkenylene, alkynylene arylene, heteroaralkenylene, heteroaralkyleneOne of an alkylene group, an alkyleneheteroarylalkylenealkylene group, an alkyleneheteroarylalkylene group, an alkyleneheteroarylalkenylene group, an alkynyleneheteroarylalkylene group, or an alkynyleneheteroarylalkynylene group;
each W2Is one of a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, an alkylheteroalkyl group, an alkynyl group, a hydrocarbylene group, a hydrocarbyleneheteroalkylene group, an alkenylene group, a hydrocarbyleneheteroalkylene group, an alkynylene group or a hydrocarbyleneheteroalkynylene group;
the epoxy resin is at least one of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin and novolac epoxy resin;
the auxiliary material is at least one of an accelerator, a diluent, a toughening agent, a thickening agent, an adhesion promoter, a whitening agent, a pigment, an addition component, a coupling agent, a filler, a thixotropic agent and an antioxidant;
said reinforcing material is a fibrous or non-fibrous material; the fiber material is at least one of glass fiber, carbon fiber, natural fiber and chemical fiber; the non-fibrous material is at least one of carbon nanotubes, carbon black, metal nanoparticles, organic nanoparticles, iron oxide and boron nitride;
the solvent is acetone, propyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide or xylene.
2. A method for recycling the recyclable copper clad laminate according to claim 1, comprising a step of degrading the degradable epoxy resin matrix with an acid and a solvent.
3. The recovery method according to claim 2, wherein the degradation is carried out under heating.
4. The recovery method according to claim 2, wherein the acid is at least one of hydrochloric acid, hydrobromic acid, hydrofluoric acid, acetic acid, trifluoroacetic acid, lactic acid, formic acid, propionic acid, citric acid, methanesulfonic acid, p-toluenesulfonic acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, perchloric acid, benzoic acid, salicylic acid, phthalic acid.
5. The recovery method according to claim 2, wherein the solvent is at least one of methanol, ethanol, ethylene glycol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, hexanol, heptanol, octanol, nonanol, benzyl alcohol, phenethyl alcohol, p-dimethylolbenzene, m-dimethylolbenzene, o-dimethylolbenzene, p-dihydroxyethylbenzene, m-dihydroxyethylbenzene, o-dihydroxyethylbenzene, water, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, methyltetrahydrofuran, glycerol, and dioxane.
6. The recovery method according to claim 2, wherein the concentration of the acid is 0.1 to 90 wt%.
7. The recovery method according to claim 2, wherein the concentration of the acid is 10 to 20 wt%.
8. The recycling method according to claim 3, wherein the heating temperature is 15 to 400 ℃ and the heating time is 1 to 120 hours.
9. The recycling method according to claim 3, wherein the heating temperature is 80 to 120 ℃ and the heating time is 4 to 8 hours.
10. The recovery method according to claim 2, further comprising a step of recovering the degradation products by neutralization, filtration and/or precipitation.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410781355.9A CN104527177B (en) | 2014-12-16 | 2014-12-16 | A kind of recyclable prepreg, cured sheets, copper-clad plate and its preparation for printed circuit board (PCB), recovery method |
| PCT/CN2015/097551 WO2016095817A1 (en) | 2014-12-16 | 2015-12-16 | Recyclable copper clad laminates containing fiber composition |
| US15/534,960 US10486394B2 (en) | 2014-12-16 | 2015-12-16 | Recyclable copper clad laminates containing fiber composition |
| EP15869324.2A EP3233484A4 (en) | 2014-12-16 | 2015-12-16 | Recyclable copper clad laminates containing fiber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410781355.9A CN104527177B (en) | 2014-12-16 | 2014-12-16 | A kind of recyclable prepreg, cured sheets, copper-clad plate and its preparation for printed circuit board (PCB), recovery method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104527177A CN104527177A (en) | 2015-04-22 |
| CN104527177B true CN104527177B (en) | 2018-03-23 |
Family
ID=52842897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410781355.9A Active CN104527177B (en) | 2014-12-16 | 2014-12-16 | A kind of recyclable prepreg, cured sheets, copper-clad plate and its preparation for printed circuit board (PCB), recovery method |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US10486394B2 (en) |
| EP (1) | EP3233484A4 (en) |
| CN (1) | CN104527177B (en) |
| WO (1) | WO2016095817A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104527177B (en) * | 2014-12-16 | 2018-03-23 | 艾达索高新材料芜湖有限公司 | A kind of recyclable prepreg, cured sheets, copper-clad plate and its preparation for printed circuit board (PCB), recovery method |
| CN104845304B (en) * | 2015-04-21 | 2016-10-05 | 环境保护部华南环境科学研究所 | A kind of method utilizing copper-clad plate residue as resources to recycle |
| MY197994A (en) * | 2016-04-05 | 2023-07-25 | Composite Tech Holdings Ltd | Recycling of polymer matrix composite |
| CN106632996B (en) * | 2016-12-21 | 2019-07-23 | 芜湖天道绿色新材料有限公司 | Composition epoxy resin, preparation method and the recovery method of fiber reinforcement auto parts and components rapid shaping |
| CN106832767B (en) * | 2016-12-21 | 2019-08-06 | 芜湖天道绿色新材料有限公司 | Degradable composition epoxy resin, preparation method and the recovery method of fiber reinforcement priming by vacuum |
| CN106750182B (en) * | 2016-12-29 | 2019-06-14 | 广东生益科技股份有限公司 | A kind of degradable resin composition and its prepreg, laminate and its recovery method of preparation |
| CN109206646A (en) * | 2018-08-14 | 2019-01-15 | 艾达索高新材料芜湖有限公司 | A kind of degradable epoxy chopped carbon fiber felt prepreg and its production technology |
| CN111057270B (en) * | 2019-12-04 | 2021-08-31 | 广东盈骅新材料科技有限公司 | Modified carbon black and preparation method thereof, resin composition and copper-clad plate |
| CN113459638A (en) * | 2021-07-19 | 2021-10-01 | 安徽绿洲危险废物综合利用有限公司 | Waste copper-clad plate insulation board regenerated substrate and preparation method thereof |
| US20230379717A1 (en) | 2021-08-31 | 2023-11-23 | Suzhou Institute Of Nano-Tech And Nano-Bionics (Sinano) . Chinese Academy Of Sciences | Credential handling of an iot safe applet |
| CN114479177B (en) * | 2022-02-24 | 2024-01-16 | 宁夏大学 | Epoxy resin degradation method, epoxy resin degradation solvent system and recovery method |
| WO2024121807A1 (en) * | 2022-12-08 | 2024-06-13 | Ctp Advanced Materials Gmbh. | Recyclable sandwich structure composites |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS568227A (en) * | 1979-06-29 | 1981-01-28 | Kanegafuchi Chem Ind Co Ltd | Continuous preparation of laminate covered by metal foil |
| JP3489025B2 (en) * | 2000-01-14 | 2004-01-19 | 大塚化学ホールディングス株式会社 | Epoxy resin composition and electronic component using the same |
| CN101368077B (en) * | 2008-10-09 | 2011-11-30 | 腾辉电子（苏州）有限公司 | Epoxy resin adhesive liquid |
| CN101735562B (en) * | 2009-12-11 | 2012-09-26 | 广东生益科技股份有限公司 | Epoxy resin composition, preparation method thereof, laminated material and copper-clad laminated board manufactured by adopting epoxy resin composition |
| CN102069615A (en) * | 2010-11-11 | 2011-05-25 | 广东生益科技股份有限公司 | Fabrication method of copper-clad plate |
| ES2675856T3 (en) * | 2010-11-30 | 2018-07-13 | Connora Technologies, Inc. | New agents for reworkable epoxy resins |
| CN103012747A (en) * | 2012-12-28 | 2013-04-03 | 艾达索高新材料无锡有限公司 | Degradable mixed polyamine epoxy resin curing agent, and preparation and composite material recovery thereof |
| CN103059517A (en) | 2012-12-31 | 2013-04-24 | 金安国纪科技股份有限公司 | Environmentally-friendly copper-clad plate glue solution, copper-clad plate and preparation method thereof |
| CN103242509B (en) * | 2013-04-18 | 2015-06-10 | 艾达索高新材料无锡有限公司 | Degradable cyclic acetal and cyclic ketal diamine epoxy resin curing agent and application thereof |
| CN103254406B (en) * | 2013-04-18 | 2016-03-30 | 艾达索高新材料无锡有限公司 | The organic aromatic amine of degradable and organic fragrant ammonium salt class incubated epoxide curing agent and application thereof |
| CN103193959B (en) * | 2013-04-18 | 2014-07-30 | 艾达索高新材料无锡有限公司 | Degradable hydrazide latent epoxy resin curing agent and application thereof |
| EA201501030A1 (en) * | 2013-04-18 | 2016-07-29 | Адессо Адвансд Материалз Вукси Ко., Лтд. | NEW SCRAPERS AND DECOMPASED POLYMERS AND COMPOSITES ON THEIR BASIS |
| CN103483554B (en) * | 2013-09-24 | 2015-12-02 | 艾达索高新材料无锡有限公司 | Degradable hydrazone based epoxy resin curing agent and application thereof |
| CN104530390A (en) * | 2014-12-11 | 2015-04-22 | 广东生益科技股份有限公司 | Degradable resin composition, as well as prepreg, laminated board and copper-clad plate using degradable resin composition, and degradation method of degradable resin composition |
| CN104527177B (en) * | 2014-12-16 | 2018-03-23 | 艾达索高新材料芜湖有限公司 | A kind of recyclable prepreg, cured sheets, copper-clad plate and its preparation for printed circuit board (PCB), recovery method |
-
2014
- 2014-12-16 CN CN201410781355.9A patent/CN104527177B/en active Active
-
2015
- 2015-12-16 EP EP15869324.2A patent/EP3233484A4/en not_active Withdrawn
- 2015-12-16 WO PCT/CN2015/097551 patent/WO2016095817A1/en active Application Filing
- 2015-12-16 US US15/534,960 patent/US10486394B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104527177A (en) | 2015-04-22 |
| EP3233484A1 (en) | 2017-10-25 |
| US10486394B2 (en) | 2019-11-26 |
| WO2016095817A1 (en) | 2016-06-23 |
| US20170368800A1 (en) | 2017-12-28 |
| EP3233484A4 (en) | 2018-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104527177B (en) | A kind of recyclable prepreg, cured sheets, copper-clad plate and its preparation for printed circuit board (PCB), recovery method | |
| KR101383434B1 (en) | Epoxy resin composition, prepreg, cured body, sheet-like molded body, laminate and multilayer laminate | |
| TWI410441B (en) | Epoxide resin composition, prepreg, foil with resin, resin sheet, laminated sheet and multilayer board | |
| KR100709149B1 (en) | Epoxy Resin Composition | |
| CN106916418B (en) | Thermosetting resin composition, prepreg, metal foil-clad laminate and printed circuit board | |
| JP5311823B2 (en) | Polyamide resin, epoxy resin composition and cured product thereof | |
| KR20110055587A (en) | Laminate and method for producing laminate | |
| US4882216A (en) | Epoxy resin film covered with metal foil and flexible printed wiring board | |
| JP2007204598A (en) | Resin composition and cured product thereof | |
| WO2017092471A1 (en) | Thermosetting alkyl polyol glycidyl ether resin composition and application thereof | |
| JP4616771B2 (en) | Flame retardant epoxy resin composition and cured product thereof | |
| CN103813612A (en) | Metal-clad laminate, printed wiring board, and multilayer printed wiring board | |
| CN113912981A (en) | High-heat-resistance medium-Tg copper-clad plate and preparation method thereof | |
| KR101641824B1 (en) | Halogen-free thermosetting resin composition, and prepreg and laminate for printed circuits using the same | |
| CN101684181B (en) | Photosensitive polyimide and flexible printed circuit board thereof | |
| JPWO2008072630A1 (en) | Polyamide resin, epoxy resin composition using the same, and use thereof | |
| KR20120051591A (en) | Polyimide precursor resin solution | |
| CN112694623B (en) | Resin glue solution, prepreg and metal foil-clad laminate | |
| CN113831852A (en) | Glue-coated copper foil and preparation method and application thereof | |
| CN110239164B (en) | High-heat-resistance middle-Tg copper-clad plate and preparation method thereof | |
| JPH0434565B2 (en) | ||
| CN107098795B (en) | Difunctional alkenyl phenoxy compound, preparation method thereof and soluble bismaleimide resin modified by difunctional alkenyl phenoxy compound | |
| JP4919659B2 (en) | Polyamide resin composition, epoxy resin composition and use thereof | |
| CN110996536A (en) | Carrier copper foil and preparation method and application thereof | |
| JP3396578B2 (en) | Prepreg and copper-clad laminate using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 241000, Anhui, Wuhu Three Hill Road, No. 15, road, three hills, science and technology innovation center, No. 4 factory building Applicant after: ADESSO ADVANCED MATERIALS WUHU CO.,LTD. Address before: Huihong Industrial Park No. 18 Xishilu District 214028 Jiangsu city of Wuxi Province Applicant before: ADESSO ADVANCED MATERIALS WUXI Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231218 Address after: No. 305, Floor 3, 5G Acceleration Port, Building 33, Lufeng Heyuan, No. 328, Xiaoxiang Middle Road, Yuelu Street, Yuelu District, Changsha, Hunan 410000 Patentee after: Changsha Adaso High tech Materials Co.,Ltd. Address before: Building 4, Sanshan Technology Entrepreneurship Center, No. 15 Exi Road, Sanshan District, Wuhu City, Anhui Province, 241000 Patentee before: ADESSO ADVANCED MATERIALS WUHU CO.,LTD. |
|
| TR01 | Transfer of patent right |